CN104137274A - Conductive paste for solar cell electrodes, solar cell, and method for manufacturing solar cell - Google Patents
Conductive paste for solar cell electrodes, solar cell, and method for manufacturing solar cell Download PDFInfo
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- CN104137274A CN104137274A CN201380011267.4A CN201380011267A CN104137274A CN 104137274 A CN104137274 A CN 104137274A CN 201380011267 A CN201380011267 A CN 201380011267A CN 104137274 A CN104137274 A CN 104137274A
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- electrode
- solar cell
- metal element
- semiconductor substrate
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- 238000000034 method Methods 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000758 substrate Substances 0.000 claims abstract description 141
- 239000004065 semiconductor Substances 0.000 claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 claims abstract description 99
- 239000002184 metal Substances 0.000 claims abstract description 95
- 239000011521 glass Substances 0.000 claims abstract description 83
- 229910052709 silver Inorganic materials 0.000 claims abstract description 58
- 239000010948 rhodium Substances 0.000 claims abstract description 57
- 239000004332 silver Substances 0.000 claims abstract description 56
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 55
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 239000010955 niobium Substances 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 8
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 8
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000428 dust Substances 0.000 claims description 28
- 238000010304 firing Methods 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 59
- 239000010408 film Substances 0.000 description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 27
- 229910052782 aluminium Inorganic materials 0.000 description 27
- 229910052710 silicon Inorganic materials 0.000 description 27
- 239000010703 silicon Substances 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 26
- 238000002161 passivation Methods 0.000 description 25
- 239000004411 aluminium Substances 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
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- 239000000843 powder Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
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- 230000000694 effects Effects 0.000 description 13
- 229910001097 yellow gold Inorganic materials 0.000 description 13
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000002902 organometallic compounds Chemical class 0.000 description 12
- 235000011187 glycerol Nutrition 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- -1 while burning till Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000231 atomic layer deposition Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910021419 crystalline silicon Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 5
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- MWZNPHHDRLXXHO-UHFFFAOYSA-N rhodium;hydrate Chemical compound O.[Rh] MWZNPHHDRLXXHO-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 206010003084 Areflexia Diseases 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FCAKIZSNFRGYKA-UHFFFAOYSA-N [Os].C1CC=CC=C1.c1ccccc1 Chemical compound [Os].C1CC=CC=C1.c1ccccc1 FCAKIZSNFRGYKA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-AHCXROLUSA-N copper-60 Chemical compound [60Cu] RYGMFSIKBFXOCR-AHCXROLUSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002908 osmium compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Sustainable Energy (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
A conductive paste for solar cell electrodes according to one embodiment of the present invention comprises: glass frit which is composed of a plurality of glass particles; and a non-glass component which is mainly composed of silver and/or copper and to which a metal element (A1) is added. In this connection, the metal element (A1) is at least one metal selected from among vanadium, niobium, tantalum, rhodium, rhenium and osmium. A solar cell according to one embodiment of the present invention is provided with: a semiconductor substrate; an anti-reflection film that is arranged in a first region on one main surface of the semiconductor substrate; and an electrode which is formed by firing the conductive paste for electrodes and is arranged in a second region on the main surface of the semiconductor substrate, said second region being different from the first region.
Description
Technical field
The present invention relates to be used in the electrode that forms solar cell electrode conductivity paste, possess and burn till the solar cell of electrode and the manufacture method of this solar cell that this electrode conductivity paste forms.
Background technology
Now, the majority of the solar cell of use is for using the crystalline silicon solar cell of crystalline silicon substrates.In the manufacture of crystalline silicon solar cell, known following method,, first, sensitive surface side at the silicon substrate of a conductivity type forms after reverse conductive layer and antireflection film, at roughly whole the printing conductive paste respectively of at least a portion of antireflection film and the non-sensitive surface side of silicon substrate.Afterwards, burn till printed conductivity paste and form the surface electrode of sensitive surface side and the backplate of non-sensitive surface side.
For example having used in the solar cell of p-type silicon substrate, the conductivity paste (following, to be called silver paste agent) using silver as principal component is used in to form the electrode conductivity paste of surface electrode.In the formation operation of surface electrode, in sintering process, utilize the following phenomenon of grilling thoroughly that is called as,, by making an addition to that the antireflection film that is present under conductivity paste is removed in the effect melting of glass dust of conductivity paste and become ohmic contact between metal ingredient that can be in conductivity paste and silicon substrate.
The desired characteristic of surface electrode mainly contains electrical characteristics (contact resistance and wiring resistance are little etc.) and mechanical property (large etc. with the adhesive strength of substrate and inner lead).The product representation of short circuit current, open circuit voltage and fill factor, curve factor (FF (Fill Factor)) for the electricity output of solar cell, but contact resistance and wiring resistance likely become the principal element that determines FF.
In order to form the electrode that has improved above-mentioned each characteristic, the conductivity paste of various electrodes formation use is disclosed.For example, in Japanese kokai publication hei 11-213754 communique, disclose to the conductivity paste that is added with chloride, bromide and fluoride in using silver powder, glass powder, organic carrier and organic solvent etc. as the conductivity paste of composition.In addition, for example, in Japanese Unexamined Patent Application Publication 2011-519150 communique, disclose that electroconductive particle contains silver particles and the grid electrode conductivity paste of the solar cell of the metallic selected from the group being made up of Pd, Ir, Pt, Ru, Ti and Co.
Summary of the invention
The problem that invention will solve
But possessing in the solar cell of the electrode forming with silver paste agent in the past, the electrical characteristics such as the contact resistance of electrode are insufficient, expect further to improve electrical characteristics.
The present invention puts in view of the above-mentioned problems and invents, and its main purpose is to provide a kind of can reduce the contact resistance of electrode and to improving the useful electrode conductivity paste of the electrical characteristics of solar cell, possessing to have and burn till the solar cell of electrode and the manufacture method of solar cell that this electrode conductivity paste forms.
For solving the means of problem
The electrode conductivity paste of the solar cell that in order to achieve the above object, a mode of the present invention relates to has: the glass dust being made up of most glass particles; Using at least one in silver and copper as principal component and be added with the non-glass composition of metal element A 1.Wherein, at least one for selecting from vanadium, niobium, tantalum, rhodium, rhenium, osmium of metal element A 1.
In addition, the solar cell that a mode of the present invention relates to possesses: semiconductor substrate; Be disposed at the antireflection film of the first area on an interarea of this semiconductor substrate; Be disposed at the electrode that electrode conductivity paste second area, that burn till above-mentioned solar cell in conduct on an interarea of the described semiconductor substrate region different from first area forms.
In addition, a mode of the present invention relates to the manufacture method of solar cell, wherein, described solar cell possesses: semiconductor substrate, be disposed at the first area on an interarea of this semiconductor substrate antireflection film, be disposed at the electrode of the second area in conduct on an interarea of the described semiconductor substrate region different from first area, the manufacture method of described solar cell has: the first operation that forms described antireflection film on an interarea of described semiconductor substrate; The electrode of above-mentioned solar cell is disposed to the second operation on described antireflection film with conductivity paste with electrode pattern; Remove by burning till described electrode conductivity paste the described antireflection film being positioned under this electrode conductivity paste, described antireflection film is disposed to the described first area of described semiconductor substrate, and forms the 3rd operation of described electrode conductivity paste being burnt till to the described electrode forming at the described second area of described semiconductor substrate.
Invention effect
According to the manufacture method of conductivity paste, solar cell and solar cell for the electrode of the solar cell of above-mentioned formation, can provide the solar cell of the electrical characteristics and the reliability that have improved solar cell.
Brief description of the drawings
Fig. 1 is the schematic top plan view of observing an example of the solar cell that a mode of the present invention relates to from sensitive surface side.
Fig. 2 is the schematic top plan view of observing an example of the solar cell that a mode of the present invention relates to from non-sensitive surface side.
Fig. 3 is the figure that schematically shows an example of the solar cell that a mode of the present invention relates to, and is the cutaway view that the region that represents at the chain-dotted line of the K-K line with Fig. 1 is blocked.
Fig. 4 (a)～(e) is the cutaway view that schematically shows respectively the solar cell of an example of the manufacture method of the solar cell that a mode of the present invention relates to.
Fig. 5 is the schematic top plan view of an example of the solar cell that relates to of a mode of the present invention observed from rear side.
Fig. 6 is the schematic diagram of an example of the solar cell that represents that a mode of the present invention relates to, is the cutaway view that the region that represents at the chain-dotted line of the L-L line with Fig. 5 is blocked.
Fig. 7 is the curve chart that represents the relation of rhodium content and photoelectric conversion efficiency.
Fig. 8 is the curve chart that represents the relation of content of vanadium and FF sustainment rate.
Symbol description
1-semiconductor substrate
2-mono-conductive layer
The reverse conductive layer of 3-
4-anti-reflection layer (antireflection film)
5-surface electrode
Electrode is taken out in the output of 5a-surface
5b-surface collecting electrodes
5c-auxiliary electrode
6-backplate
Electrode is taken out in the output of the 6a-back side
6b-back side collecting electrodes
7,14-BSF region
9a-surface (sensitive surface)
The 9b-back side (non-sensitive surface)
9c-side
10-solar cell device (solar cell)
11-the first passivation layer
12-the second passivation layer
Embodiment
Below, with reference to accompanying drawing to conductivity paste for the electrode of the solar cell the present invention relates to (following, to be called conductivity paste), used the solar cell of this conductivity paste and the mode example of manufacture method thereof to be elaborated.It should be noted that, the parts of the same title that forms solar cell are accompanied by same mark.In addition, accompanying drawing is the figure schematically showing, and therefore, size and the position relationship etc. of the inscape of accompanying drawing be suitable change likely.In addition, Fig. 6 is not in order to be simply accompanied by hachure to a part for inscape.
< conductivity paste >
The conductivity paste using in the present embodiment contains: the glass dust being formed by most glass particles, using silver and copper at least one as principal component and be added with following metal element A 1, as non-glass composition and the organic carrier etc. of conductive compositions.At this, " principal component " refers to composition more than 50 mass parts when conductive compositions is made as to 100 mass parts.In addition, at least one for selecting from vanadium, niobium, tantalum, rhodium, rhenium, osmium of metal element A 1.
At this, metal element A 1 can be added with monomer, alloy or compound.In the situation that adding metal element A 1 as compound, the inorganic compound such as hydrate or oxide or the organic compound of at least one formation selected from vfanadium compound, niobium compound, tantalum compound, rhodium compound, rhenium compound and osmium compound of serving as reasons.
Especially, in the situation that adding metal element A 1 as organo-metallic compound, as this organo-metallic compound, for there is the organo-metallic compound of key of carbon and metal element A 1 in its molecular structure, for example, π-cyclopentadienyl group-divinyl rhodium, eight (carbonyl) two rhodiums, (benzene)-(1,3-cyclohexadiene) osmium, in addition, be the M as acetylene-derivative (C ≡ C-R)
nthe organo-metallic compound that (M is metal element A 1, and R is alkyl, and n is positive integer) is represented etc.And, in this case, in diethylene glycol monobutyl ether equal solvent, add above-mentioned organo-metallic compound and make its dissolving and make organo-metallic compound and contain body.It should be noted that, with regard to the content of the metal element A 1 in 100 mass parts that contain body with regard to this organo-metallic compound, 1～10 mass parts left and right is best, with regard to the content of the above-mentioned organo-metallic compound in 100 mass parts that contain body with regard to organo-metallic compound, 50～90 mass parts left and right are best.The organo-metallic compound that contains metal element A 1 with the form of organo-metallic compound according to above-mentioned making contains body, can make metal element A 1 fine dispersion in conductivity paste.
The content of at least one of above-mentioned monomer, alloy and compound is as tenor, and in the case of the silver (or copper or Kufil) that becomes principal component is made as 100 mass parts, it is above and below 1 mass parts that it is preferably 0.06 mass parts.This is because the effect of the photoelectric conversion efficiency of the solar cell that can fully be improved.These additives can add with the state of the powder of average grain diameter 40 μ m left and right, also can add and these additives be added to the liquid such as diethylene glycol monobutyl ether acetate and carried out stirring the mixture obtaining.
And then, using rhodium hydrate (Rh
2o
35H
2o) in the situation as inorganic compound, especially excellence is therefore preferred in the following areas,, is not easy aggegation and easily dispersed in conductivity paste in conductivity paste that is.Therefore, in the case of the electrode formation that conductivity paste is used in to the solar cell with semiconductor substrate, at the electrode forming and the interface of semiconductor substrate, can make ohmic contact good, thereby can further improve the photoelectric conversion efficiency of solar cell.
In addition, in non-glass composition, particularly preferably following metal element A 2 and following metal element A 3 are added as metal element A 1.At this, metal element A 2 refers at least one that select from vanadium, niobium, tantalum.In addition, metal element A 3 refers at least one that select from rhodium, rhenium, osmium.
Further preferably, be added with vanadium and rhodium as metal element A 1.
In the situation that silver (or copper or yellow gold) is made as to 100 mass parts, the content of metal element A 2 is that 0.25 mass parts left and right is best as tenor, more than being preferably 0.05 mass parts and below 1 mass parts.In addition, in the situation that silver (or copper or yellow gold) is made as to 100 mass parts, the content of metal element A 3 is that 0.07 mass parts left and right is best as tenor, more than being preferably 0.06 mass parts and below 0.5 mass parts.This is because in above-mentioned number range, can expect to improve the reliability of solar cell, thereby can suppress the reduction of the initial stage characteristic (especially FF value) of solar cell.
In these metal element A 2 and metal element A 3, the value that can be 50% particle size (D50) in the aggregate-value of all particles of these elements (accumulative total mass percent) is that the powder state of 0.05～20 μ m left and right uses, and also can use in the liquid such as diethylene glycol monobutyl ether acetate and add such powder and the mixture of stirring.If for example vanadium of metal element A 2, preferably with vanadium oxide (V
2o
5) etc. the powder of oxide add.If for example rhodium of metal element A 3, preferably with rhodium hydrate (Rh
2o
35H
2etc. O) hydrate adds.This hydrate is not easy to produce aggegation in conductivity paste, and easily to especially excellent aspect homodisperse in conductivity paste.In addition, metal element A 2 and metal element A 3 can be used as organo-metallic compound interpolation as described above.
Silver (or copper or yellow gold) as the principal component as conductivity paste using is in the present embodiment not specially limited the shape in powder, can use the powder such as spherical or laminar.In addition, the particle diameter of these powder is according to the coating of conductivity paste (printing) condition and the suitable selection of firing condition, and from printing and burn till the viewpoint of characteristic, the powder of 0.1～10 μ m left and right is applicable to.
It should be noted that, as the metallic element of the principal component in conductivity paste, can further contain nickel with respect to silver and copper.In this case, with respect to silver-colored 100 mass parts, more than containing copper 10 mass parts and below 135 mass parts, and more than containing nickel 1 mass parts and below 15 mass parts.Be more preferably, with respect to silver-colored 100 mass parts, more than containing copper 60 mass parts and below 120 mass parts, and more than containing nickel 7 mass parts and below 11 mass parts.And, in this case, preferably, in the case of the total mass parts of silver, copper and nickel is made as 100 mass parts, contain above-mentioned metal element A 1, A2, A3 with the number range of above-mentioned mass parts.
In addition, about the composition of glass dust, as glass material, for example, except using Al
2o
3-SiO
2-PbO system, PbO-SiO
2-B
2o
3system, PbO-SiO
2system or SiO
2-Bi
2o
3the lead such as-PbO system are beyond glass, also can use B
2o
3-SiO
2-Bi
2o
3system or B
2o
3-SiO
2the non-lead such as-ZnO system are glass.
In addition, preferably at least one party's the surface that forms glass particle and silver or the copper etc. of these glass dust and become the metallic of principal component, load has above-mentioned metal element A 1.Especially the area load that, preferably becomes at least one party's of the metallic of principal component particle at glass particle and silver or copper etc. has metal element A 2 and metal element A 3.
Thus, concentration in the conductivity paste that metal element A 2 and the aggegation of metal element A 3 etc. can suppress to make due to conductivity paste time causes inhomogeneous, thus metal element A 2 and metal element A 3 disperseing more uniformly to conductivity paste can be formed.And then, by at glass particle and become at least one party's of the metallic of principal component particle surface carried metal elements A 2, in the electrode forming, can and become between the metallic of principal component at glass dust and easily form the bonding via metal element A 2, with respect to the structure of glass dust and metallic Direct Bonding, can form stable and strong structure.So, can improve thus the long-term reliability of solar cell.And then by the load of metal element A 3, can suppress the reduction of the ohmic contact of electrode and semiconductor substrate, thereby can suppress the reduction of the photoelectric conversion efficiency at initial stage.
Carry out the load of metal element A 1, metal element A 2 and metal element A 3 for example carries out with deposition-precipitation method to the surface of the metallics such as glass particle and silver or copper.In addition, preferably there is metal element A 1 at the area load of glass particle.That is, by the area load metal element A 1 at glass particle, while burning till, glass ingredient forms glassy layer at silicon face, therefore can more improve the effect of improving of ohmic contact based on metal element A 1.Same preferred area load metal element A 2 and metal element A 3 at glass particle.At this, about load, the state that the phase counterdiffusion of element do not occurred to for the surface of the metallic such as surface or silver or copper of glass particle and the abutment portion of metal element A 1, metal element A 2 and metal element A 3 is called the state of load.And this state can be distinguished by the elementary analysis of abutment portion.
In addition, as making metal element A 1, metal element A 2 and metal element A 3 to homodisperse method in conductivity paste, except the above-mentioned method based on load, for example, can mix to glycerine or ethylene glycol, and then, at least one of mix and blend glass dust and silver and copper.
To the method, describe as an example of rhodium example as metal element A 1.
(1) first, prepare emboliform rhodium.Preferably the particle diameter of this rhodium particle is below 10nm.So using the particle of the less particle diameter below 10nm is for rhodium is dispersed in conductivity paste as far as possible.
(2) by slowly being put into pure water and stir, this rhodium particle make its dispersion make disperse water.With regard to the amount of the rhodium particle in this disperse water, with respect to pure water 100g, rhodium particle is 0.1～0.3g left and right.Like this, first rhodium particle being put into pure water and making disperse water is because of following reason, that is, and and in the case of directly the rhodium particle below particle diameter 10nm being put into glycerine or ethylene glycol, the aggegation in glycerine or ethylene glycol of rhodium particle, and can not make well dispersion liquid.
(3) then, glycerine or ethylene glycol are put into above-mentioned disperse water and is uniformly mixed.With regard to the amount of glycerine now or ethylene glycol, with respect to disperse water 100 mass parts, be preferably 5～20 mass parts left and right.At this, use glycerine or ethylene glycol to be because soluble and terpinol or the diethylene glycol monobutyl ether etc. of the solvent as in conductivity paste are also easily dissolved to the water capacity.; in solubility parameter (SP value); 23.4) and diethylene glycol monobutyl ether (SP value: SP value is variant 8.9) etc. water (SP value:; mutually be not easy to dissolve; therefore in the situation that directly disperse water being put into conductivity paste; can not make rhodium particle dispersed in conductivity paste; 17.2) or ethylene glycol (SP value: 14.2) there is the SP value between the SP value of water and diethylene glycol monobutyl ether etc. but glycerine (SP value:; therefore, all dissolve well for water and diethylene glycol monobutyl ether.
(4) become 100 DEG C of left and right with the heating liquid of glycerine or ethylene glycol by being mixed with above-mentioned disperse water, evaporate the water.Confirm to add and hanker that moisture evaporates completely and the quality of liquid does not change and stop this heating at this.Thus, carry out the displacement of solvent, making rhodium particle is roughly dispersed in the dispersion liquid of glycerine or ethylene glycol.
(5) then, by the paste of mixing at least one and glass dust and the organic carrier that have silver and copper, mix and blend makes rhodium particle be scattered in the dispersion liquid in above-mentioned glycerine or ethylene glycol.Thus, can make rhodium particle be dispersed in conductivity paste.
In addition, as the adding method of metal element A 2, can be that value 50%, particle size (D50) is that the powder of 0.05～20 about μ m directly adds in paste by the aggregate-value of all particles of metallic (aggregate-value mass percent).But, as described above, if being included in glass particle, it adds, can realize metal element A 2 to the uniform dispersion in conductivity paste, and therefore preferred.
And then, the silver (or copper or yellow gold) contained with respect to the conductivity paste of present embodiment contain quality 100 mass parts, the quality that contains of preferred glass powder is that 1 mass parts is above and below 15 mass parts, and above and 6.5 mass parts of 4.5 mass parts be the best below.Be made as in above-mentioned number range by containing quality, it is good that the adhesive strength of semiconductor substrate and electrode and contact resistance become.
Organic carrier obtains by the resinous principle using as adhesive is dissolved in to organic solvent.As organic bond, use cellulose-based resin, acrylic resin or alkyd resins etc., as organic solvent, for example, use terpinol, diethylene glycol monobutyl ether acetate etc.According to present embodiment, by adding metal element A 2, in the electrode forming, between glass dust and silver (or copper or yellow gold), form the bonding via metal element A 2, with respect to glass dust in the past and the structure of silver (or copper or yellow gold) Direct Bonding, can form stable and strong structure.Thus, can improve the long-term reliability of solar cell.
In addition, especially preferably make metal element A 2 be included in the glass particle that forms glass dust.This is due to following reason,, can make thus metal element A 2 be dispersed in conductivity paste and make with the counterdiffusion of silicon phase the metallic such as glass particle composition and silver or copper between bonding become firm, can make the bonding stabilisation between silicon and electrode, thereby more improve the reliability of solar cell device.In this case, in the situation that glass dust is made as to 100 mass parts, the content of metal element A 2 is that 5 mass parts left and right are best as tenor, more than being preferably 0.2 mass parts and below 20 mass parts.This is because in above-mentioned number range, can expect to improve the reliability of solar cell, thereby suppress the reduction of the initial stage characteristic (especially FF value) of solar cell.
And then by adding metal element A 3, can suppress the reduction of the ohmic contact of the electrode that forms with the interpolation of metal element A 2 and silicon substrate, thereby can suppress the reduction of the photoelectric conversion efficiency at initial stage.
Especially in the present embodiment, as described above, in conductivity paste, using silver (or copper or yellow gold) as principal component and be added with above-mentioned metal element A 2 and above-mentioned metal element A 3, therefore these catalytic action can promote the melting of the antireflection film based on glass dust and the effect of removing, improve the output characteristic (especially fill factor, curve factor (FF)) of solar cell, thereby can improve its photoelectric conversion efficiency.
The basic structure > of < solar cell device
The basic structure of the solar cell device to the mode as solar cell describes.As shown in Figures 1 to 3, solar cell device 10 has as surface (upper surface of sensitive surface, Fig. 3) 9a of an interarea of light incident with as the back side (lower surface of non-sensitive surface, Fig. 3) 9b of its opposing face.In addition, solar cell device 10 possess be arranged at the surperficial 9a of semiconductor substrate 1 upper, as anti-reflection layer 4 and the surface electrode 5 of antireflection film, and be arranged at the backplate 6 on the back side 9b of semiconductor substrate 1.It should be noted that, semiconductor substrate 1 has a conductive layer 2 and is arranged at the reverse conductive layer 3 of its surperficial 9a side.
The concrete example > of < solar cell device
Then, the concrete example of solar cell device is described.As semiconductor substrate 1, suitable use has the dopant element of regulation and is the crystalline silicon substrates such as monocrystalline silicon substrate or polycrystalline silicon substrate of a conductivity type (such as p-type).The resistivity of semiconductor substrate 1 is 0.8～2.5 Ω cm left and right.In addition, the thickness of semiconductor substrate 1 is for example made as 250 μ m below for good, and then is preferably made as below 150 μ m.In addition, the flat shape of semiconductor substrate 1 is not specially limited, as long as for quadrangle shape, method for making and arrange most solar cell devices and viewpoint while forming solar module etc., for preferably.
To using p-type silicon substrate to describe as the example of semiconductor substrate 1.As long as situation about forming for be the mode of p-type with semiconductor substrate 1, as dopant element, it is good for example adding boron or gallium.
The reverse conductive layer 3 that forms pn knot with a conductive layer 2 is the layer being with respect to the reverse conductivity type of a conductive layer 2 (semiconductor substrate 1), is made as the surperficial 9a side in semiconductor substrate 1.If a conductive layer 2 is for being the conductivity type of p-type, oppositely conductive layer 3 forms in the mode of the conductivity type that is N-shaped.The conductivity type that is p-type at semiconductor substrate 1, oppositely conductive layer 3 can form by dopant elements such as the surperficial 9a side diffusion phosphorus to semiconductor substrate 1.
Anti-reflection layer 4 reduces the reflection of light rate of surperficial 9a and increases the amount of the light that semiconductor substrate 1 absorbs.And, by increasing the electron hole pair generating due to light absorption, contribute to improve the conversion efficiency of solar cell.Anti-reflection layer 4 is for example made up of silicon nitride film, oxidation titanium film, silicon oxide film or pellumina or their stacked film.The thickness of anti-reflection layer 4, according to the suitable selection of material forming, can be realized the mode of areflexia condition and set with the incident light for suitable.The refractive index that is preferably formed the anti-reflection layer 4 on semiconductor substrate 1 is 1.8～2.3 left and right, and thickness is
left and right.In addition, anti-reflection layer 4 can be as minimizing because the passivating film of the reduction of the compound conversion efficiency causing of the charge carrier of interface Ji Li circle at semiconductor substrate 1 plays a role.
BSF (Back-Surface-Field: back surface field) region 7 has following effect: form internal electric field in the back side of semiconductor substrate 1 9b side, and reduce the reduction due near the compound conversion efficiency causing of charge carrier 9b overleaf.BSF region 7 is the conductivity type identical with a conductive layer 2 of semiconductor substrate 1, but has the more much higher several carrier concentrations of the majority carrier concentration containing than a conductive layer 2.This means in BSF region 7, have dopant element with the higher concentration of concentration than the dopant element that is doped in a conductive layer 2.In BSF region 7, if semiconductor substrate 1 is p-type,, for example preferably by dopant elements such as back side 9b side diffused with boron or aluminium, make the concentration of these dopant elements become 1 × 10
18～5 × 10
21atoms/cm
3left and right.
As shown in Figure 1, surface electrode 5 has surface output taking-up electrode (bus electrode) 5a and surperficial collecting electrodes (finger electrode) 5b.At least a portion of surface output taking-up electrode 5a is intersected with surperficial collecting electrodes 5b.This surface output is taken out electrode 5a and is for example had the width about 1.3～2.5mm.
With regard to surperficial collecting electrodes 5b, its live width is 50～200 μ m left and right, and it is thin that electrode 5a is taken out in specific surface output.In addition, surperficial collecting electrodes 5b is spaced from each other the interval of 1.5～3mm left and right and arranges multiple.
The thickness of surface electrode 5 is 10～40 μ m left and right.Surface electrode 5 for example can burn till and form by the conductivity paste that comprises silver (or copper or yellow gold) powder, glass dust, organic carrier etc. being applied as with screen printing etc. after the shape of expectation.Forming in surface electrode 5, burn till the glass dust melting of middle melting and remove anti-reflection layer 4, and then adhesion after reacting with the most surface of semiconductor substrate 1, formation electrically contacts with semiconductor substrate 1, and keeps mechanical adhesive strength.
Surface electrode 5 also can be made up of above-mentioned such bottom electrode layer forming and the electrode plating layer as conductive layer forming thereon with plating method.
As shown in Figure 2, backplate 6 has back side output taking-up electrode 6a and back side collecting electrodes 6b.The thickness that electrode 6a is taken out in the back side output of present embodiment is 10～30 μ m left and right, and width is 1.3～7mm left and right.Electrode 6a is taken out in back side output for example can be by burning till and form after the shape that silver (or copper or yellow gold) paste application is become to expect.In addition, with regard to the collecting electrodes 6b of the back side, thickness is 15～50 about μ m, is formed at roughly whole an of part who removes back side output and take out electrode 6a of the back side 9b of semiconductor substrate 1.This back side collecting electrodes 6b for example can be by burning till and form after the shape that aluminium paste application is become to expect.
The conductivity paste of present embodiment is also applicable to the formation that electrode 6a is taken out in back side output.The main characteristic that requires back side output to take out electrode 6a is to electrically contact with the adhesive strength of semiconductor substrate 1, with back side collecting electrodes 6b good and the resistance value of electrode itself, take out electrode 6a by using the conductivity paste of present embodiment, can form the back side output that has improved these characteristics.
The manufacture method > of < solar cell device
Secondly, the manufacture method of solar cell device 10 is described.As described above, solar cell device 10 for example possesses: the semiconductor substrate 1 being made up of silicon; Be disposed at the anti-reflection layer 4 of the first area on an interarea of this semiconductor substrate 1; Be disposed at second area on an interarea of semiconductor substrate 1, burn till the electrode that above-mentioned conductivity paste forms.The manufacture of the solar cell device 10 so forming comprises: the first operation that forms anti-reflection layer 4 on an interarea of semiconductor substrate 1; Above-mentioned conductivity paste is disposed to the second operation on anti-reflection layer 4; Remove the anti-reflection layer 4 that is positioned under this conductivity paste and anti-reflection layer 4 be disposed to the first area of semiconductor substrate 1 and form the 3rd operation of electrode at the second area of semiconductor substrate 1 by burning till above-mentioned conductivity paste.
Then, more concrete manufacture method is described.First, prepare the semiconductor substrate 1 of formation one conductive layer as shown in Fig. 4 (a).In the situation that semiconductor substrate 1 is monocrystalline silicon substrate, for example, use the formation such as FZ (float-zone method) method or CZ (Czoncharlski method) method.In the situation that semiconductor substrate 1 is polycrystalline silicon substrate, for example, with formation such as castings.It should be noted that, below, be that example describes with the polysilicon of p-type.
At first, for example manufacture the ingot bar of polysilicon with casting.Then, this ingot bar is for example cut into the thickness below 250 μ m and makes semiconductor substrate 1.Afterwards, in order to remove mechanical injuries layer and the pollution layer of truncation surface of semiconductor substrate 1, preferably with solution such as NaOH, KOH or hydrofluoric acid-nitric acid, denier etching is carried out in surface.It should be noted that, preferably after this etching work procedure, form small concaveconvex structure (suede structure) on the surface of semiconductor substrate 1 with wet etching or dry etching method.By forming this suede structure, can reduce the reflection of light rate of surperficial 9a, thereby improve the conversion efficiency of solar cell.In addition, according to formation method and the condition of suede structure, also can omit aforesaid damage layer and remove operation.
Then,, as shown in Fig. 4 (b), in the top layer of the surperficial 9a side of semiconductor substrate 1, form reverse conductive layer 3.These reverse conductive layer 3 use will form the P of paste state
2o
5be coated on the surface of semiconductor substrate 1 and make the coating thermal diffusion method of its thermal diffusion, will form the POCl of gaseous state
3(phosphorous oxychloride) is as formation such as the gas phase thermal diffusion method of diffuse source or ion implantation that phosphonium ion is directly spread.This reverse conductive layer 3 forms the thickness of 0.1～1 μ m left and right, the square resistance of 40～150 Ω/ left and right.It should be noted that, oppositely the formation method of conductive layer 3 is not limited to said method, for example, also can use thin film technique, the crystalline silicon film that formation contains hydrogenated amorphous silicon film or microcrystalline sillicon film etc.And then, between semiconductor substrate 1 and reverse conductive layer 3, form i type silicon area.
In the time forming reverse conductive layer 3,9b side has also formed in the situation of reverse conductive layer overleaf, and only etching is removed back side 9b side and the conductive area of p-type is exposed.For example, in hydrofluoric acid-salpeter solution, only flood the back side 9b side in semiconductor substrate 1 and remove reverse conductive layer 3.Afterwards, in the time forming reverse conductive layer 3, sticky paying in the surperficial phosphorus glass of semiconductor substrate 1 removed in etching.In addition, use in advance 9b side overleaf to form diffusion mask, and with reverse conductive layers 3 of formation such as gas phase thermal diffusion methods, then remove the processing of spreading mask, also can form same structure.
By more than, can prepare to possess has a conductive layer 2 and the reverse semiconductor substrate 1 of conductive layer 3.
Then,, as shown in Fig. 4 (c), form the anti-reflection layer 4 as antireflection film.The film that the formation such as anti-reflection layer 4 use PECVD (plasma enhanced chemical vapor deposition: plasma enhanced chemical vapor deposition method) method, hot CVD method, vapour deposition method or sputtering method are made up of silicon nitride, titanium oxide, silica or aluminium oxide etc.If for example form the situation of the anti-reflection layer 4 being formed by silicon nitride film by PECVD method, by being made as 500 DEG C of left and right in reative cell, and decompose and use nitrogen (N with glow discharge
2) dilution silane (Si
3h
4) and ammonia (NH
3) mixed gas plasma and make its deposition and form anti-reflection layer 4.
Then,, as shown in Fig. 4 (d), form back side collecting electrodes 6b and BSF region 7 in the back side of semiconductor substrate 1 9b side.As method for making, for example, by with after print process aluminium coat paste, burn till and aluminium is spread to semiconductor substrate 1 in 600～850 DEG C of left and right of temperature, can form back side collecting electrodes 6b and BSF region 7.If by the method for printing burnt aluminum paste, not only can form the diffusion zone of expecting at printing surface, and in the time forming reverse conductive layer 3, there is no need to remove also the reverse conductive layer of the N-shaped of 9b side formation overleaf, only the periphery of 9b side carries out pn separation (separating the join domain at pn junction surface) with laser overleaf.
As the aluminium paste that is used to form back side collecting electrodes 6b, for example, use the aluminium paste that contains metal dust, glass powder and organic carrier using aluminium as principal component to make.Remove the part at the position that forms back side output taking-up electrode 6a, this conductivity paste is coated on to roughly whole of back side 9b.As coating process, can use stencil printing etc.So, after coating electrically conductive paste, during from operation, conductivity paste is not easy the viewpoint of sticky part of paying other, preferably makes it dry at the temperature evaporating solvent specifying.
It should be noted that, the formation method in BSF region 7 is not limited to said method, can use Boron tribromide (BBr
3) method that forms in the temperature of 800～1100 DEG C of left and right as the thermal diffusion method of diffuse source, in addition, also can use thin film technique, form the crystalline silicon film that contains hydrogenated amorphous silicon film or microcrystalline sillicon film etc.And then can between a conductive layer 2 and BSF region 7, form i type silicon area.
Then,, as shown in Fig. 4 (e), form surface electrode 5 and back side output taking-up electrode 6a.
Surface electrode 5 is made of conductivity paste as described above, described conductivity paste contains: silver (or copper or yellow gold), as principal component, is added with non-glass composition, glass dust, the organic carrier of above-mentioned metal element A 2 and above-mentioned metal element A 3.This conductivity paste is applied as to the electrode pattern shape of regulation at the surperficial 9a of semiconductor substrate 1.Afterwards, on semiconductor substrate 1, form surface electrode 5 by burning till 600～850 DEG C of maximum temperatures tens of seconds～about tens of minutes.
As coating process, can use stencil printing etc.After coating electrically conductive paste, preferably make it dry at the temperature evaporating solvent specifying.By grilling thoroughly in sintering process, at high temperature glass dust reacts with anti-reflection layer 4, is electrically connected and Mechanical Contact with semiconductor substrate 1 so realize surface electrode 5.Surface electrode 5 also can be as described above made up of the bottom electrode layer forming and the electrode plating layer that forms with plating method on it.
Back side output is taken out electrode 6a and is used silver (or copper or yellow gold) paste that contains the metal dust using silver as principal component, glass dust, organic carrier to make.In advance by this silver (or copper or yellow gold) paste application in the shape of predetermining.It should be noted that, by by silver (or copper or yellow gold) paste application in the position joining with a part for aluminium paste, it is overlapping and form electrical connection that a part of electrode 6a and back side collecting electrodes 6b is taken out in back side output.As coating process, can use stencil printing etc.After this coating, preferably make it dry at the temperature evaporating solvent specifying.
In addition, in order to reduce the components number of manufacture of solar cell, preferably the above-mentioned conductivity paste using in the formation of surface electrode 5 is also used in to back side output and takes out electrode 6a.
And by semiconductor substrate 1 being burnt till tens of seconds～about tens of minutes 600～850 DEG C of maximum temperatures in firing furnace, backplate 6 is formed at the back side 9b side of semiconductor substrate 1.Can first apply back side output and take out any of electrode 6a and back side collecting electrodes 6b, in addition, can burn till simultaneously, also can first apply and burn till any and apply and burn till another again.
It should be noted that, backplate 6 can be used the film-shaped such as evaporation or sputtering method established law, or forms with plating method.
As described above, according to the conductivity paste of present embodiment and the manufacture method of solar cell device, can make the solar cell device 10 that has improved the electrical characteristics such as contact resistance, wiring resistance.
< variation 1 >
It should be noted that, the present invention is not limited to above-mentioned execution mode, as described below, can carry out within the scope of the invention many corrections and change.
For example, can passivating film be set in the back side of semiconductor substrate 1 9b side.This passivating film has the compound effect that reduces charge carrier in the 9b of the back side at the back side as semiconductor substrate 1.As passivating film, can use silicon nitride, silica, titanium oxide or aluminium oxide etc.The thickness of passivating film is formed as with PECVD method, hot CVD method, vapour deposition method or sputtering method etc.
left and right.Therefore, the structure of the back side 9b side of semiconductor substrate 1 can be used the structure for the back side 9b side of PERC (Passivated Emitter and Rear Cell: passivation emitter back side battery) structure or PERL (Passivated Emitter Rear Locally-diffused: passivation emitter back side diffusion) structure.
For conductivity paste of the present invention, be also applicable to form overleaf after passivating film, coating on the antireflection film of the first area on the surperficial 9a that is disposed at semiconductor substrate 1, burn till conductivity paste and form the operation of electrode.9b side forms after passivating film overleaf, on the anti-reflection layer 4 of surperficial 9a, apply, burn till conductivity paste, if its maximum temperature of burning till is to exceed the temperature of 800 DEG C, the effect of the passivating film at the back side reduces, but according to the conductivity paste of present embodiment, owing to containing metal element A 2 and metal element A 3, therefore can below 800 DEG C, (for example 600～780 DEG C) burn till, and do not follow the reduction of photoelectric conversion efficiency at initial stage or long-term reliability to reduce and, burn till thereby can not make the effect of passivating film reduce.
In addition, also can form at the both ends that intersect with the length direction of surperficial collecting electrodes 5b the auxiliary electrode 5c of the wire of intersecting with surperficial collecting electrodes 5b, thus, even if the part at surperficial collecting electrodes 5b produces broken string, low-resistance rising also can be fallen, and can take out electrode 5a stream electric current to surface output by other surperficial collecting electrodes 5b, be therefore good.
In addition, also same with surface electrode 5 in electrode 6 overleaf, as long as the shape of taking out electrode 6a and taking out the back side collecting electrodes 6b of multiple wire that electrode 6a intersects with back side output for having back side output, also can use bottom electrode layer and the formation of electrode plating layer.
In the formation position of the surface electrode 5 of semiconductor substrate 1, can form the region (selective emitter region) of having carried out doping with reverse conductive layer 3 same conductivity and compared with reverse conductive layer 3 higher concentration.Now, selective emitter region forms square resistance lower compared with reverse conductive layer 3.By the square resistance in lower formation selective emitter region, can reduce the contact resistance with electrode.As the example of the formation method in selective emitter region, by forming after reverse conductive layer 3 with coating thermal diffusion method or gas phase thermal diffusion method, under the remaining state of phosphorus glass with the electrode shape of surface electrode 5 matchingly to semiconductor substrate 1 irradiating laser, can spread and form again to reverse conductive layer 3 from phosphorus glass by phosphorus.
In addition, to having used silicon substrate to be illustrated as the example of semiconductor substrate, but be not limited thereto, can use chemical characteristic etc. and the similar substrate of silicon.
< variation 2 >
Fig. 5 is the schematic top plan view of further observing an example of another solar cell device 10 from back side 9b side.Fig. 6 is the cutaway view that schematically shows the structure of the A-A of Fig. 5.As shown in Figures 5 and 6, solar cell device 10 roughly forms passivation layer as feature on whole taking the surperficial 9a side at semiconductor substrate 1 and 9bCe two sides, back side side., on N-shaped semiconductor regions 3, form the first passivation layer 11 and on p-type semiconductor regions 2, form the second passivation layer 12.The first passivation layer 11 and the second passivation layer 12 for example can be by using ALD (Atomic Layer Deposition: atomic layer evaporation) method, in the whole formation simultaneously around of semiconductor substrate 1., also form at the side of semiconductor substrate 1 9c the passivation layer being formed by above-mentioned aluminium oxide etc.And then form anti-reflection layer 4 on the first passivation layer 11.
As formed the passivation layer being formed by aluminium oxide, use following method with ALD rule.
First, in film forming room, load the semiconductor substrate 1 being formed by above-mentioned polysilicon etc. and substrate temperature is heated to 100～300 DEG C.Then, the carrier gas such as the aluminum feedstocks such as trimethyl aluminium and argon gas or nitrogen are together supplied with to 0.5 second on clockwise semiconductor substrate 1, make aluminum feedstock be adsorbed in (operation 1) around semiconductor substrate 1 whole.
Then, by with 1 second in nitrogen purge film forming room, remove the aluminum feedstock in space, and remove composition (operation 2) in the aluminum feedstock that is adsorbed in semiconductor substrate 1, beyond the composition of atomic layer level absorption.
Then, the oxidant such as water or ozone gas is supplied with to 4 seconds in film forming room, remove the CH as the alkyl of the trimethyl aluminium of aluminum feedstock
3, and the not associative key of aluminium oxide is oxidized, on semiconductor substrate, form the atomic layer (operation 3) of aluminium oxide.
Then, for example, by with 1.5 seconds in nitrogen purge film forming room, remove the oxidant in space, remove beyond the aluminium oxide of atomic layer level, for example do not contribute to (operations 4) such as the oxidants that reacts.
And, by repeating from above-mentioned operation 1 to operation 4, can form the alumina layer with specific thickness.In addition, by making the oxidant using in operation 3 contain hydrogen, alumina layer easily contains hydrogen, can increase hydrogen passivation effect.
So, by use ALD method in formation the first passivation layer 11 and the second passivation layer 12, according to the small concavo-convex alumina layer that forms on semiconductor substrate 1 surface, therefore can improve surface passivation effect.In addition, by using PECVD method or sputtering method beyond ALD method to form anti-reflection layer 4, can form fast the thickness needing, thereby can boost productivity.
Then, according to following formation surface electrode 5 (electrode 5a, the first collecting electrodes 5b are taken out in the first output) and backplate 6 (electrode 6a, the second collecting electrodes 6b are taken out in the second output).
First, effects on surface electrode 5 describes.Surface electrode 5 for example as described above, uses and contains silver as principal component and be added with metal element A 2 and the conductivity paste of the non-glass composition of metal element A 3, glass dust, organic carrier is made.After using stencil printing etc. this conductivity paste to be coated on the antireflection film 4 of surperficial 9a of semiconductor substrate 1, by burn till 600～800 DEG C of maximum temperatures tens of seconds～within about tens of minutes, form surface electrode 5.
Then, BSF region 14 and backplate 6 are described.The aluminium paste that contains glass dust is applied directly to the regulation region on the second passivation layer 12, be the grilling thoroughly of high-temperature heat treatment of 600～800 DEG C by carrying out maximum temperature, the paste composition of coating is broken through the second passivation film 12, form BSF region 14 in the back side of semiconductor substrate 1 9b side, and form aluminium lamination thereon.It should be noted that, this aluminium lamination can be served as back side collecting electrodes 6b and be used.It should be noted that, as forming region, for example, in the region that a part of output taking-up electrode 6a forms overleaf, form the shape as shown in Figure 5 in the 9b of the back side.And output is taken out in the formation of electrode 6a overleaf, also preferably use and contain above-mentioned silver as principal component and be added with metal element A 2 and the conductivity paste of the non-glass composition of metal element A 3, glass dust, organic carrier is made.
As shown in Figure 5, this conductivity paste is formed to three linearities, be coated on the second passivating film 12 with its part and the mode that back side collecting electrodes 6b joins.Afterwards, tens of second by burning till 600～800 DEG C of maximum temperatures～within about tens of minutes, forms back side output taking-up electrode 6a.As coating process, can use stencil printing etc., after coating, make it dry at the temperature evaporating solvent specifying.Back side output is taken out electrode 6a by contacting with aluminium lamination, and is connected with back side collecting electrodes 6b.
It should be noted that, also can first form the back side output being formed by silver and take out electrode 6a, form afterwards the back side collecting electrodes 6b being formed by aluminium.In addition, back side output is taken out electrode 6a and need not directly be contacted with semiconductor substrate 1, takes out between electrode 6a and semiconductor substrate 1 and can have the second passivation layer 12 in the second output.
Even so in the case of semiconductor substrate 1 roughly whole form passivation layer 11,12, as described above, can burn till below at 800 DEG C, can not make the effect of passivating film reduce and burn till.
[embodiment]
Below, the specific embodiment of above-mentioned execution mode is described.
< example 1 >
First, as semiconductor substrate, having prepared multi-disc is about 156mm on one side of overlooking lower square shape, and thickness is the polycrystalline silicon substrate of approximately 200 μ m.These silicon substrates use the polycrystalline silicon substrate that is the p-type electric-conducting type of resistivity 1.5 Ω cm left and right by doped with boron.The surperficial damage layer of this silicon substrate has been carried out to etching with the NaOH aqueous solution to be cleaned.
And, formed concaveconvex structure (suede structure) in the RIE for face side of each silicon substrate (Reactive Ion Etching: active-ion-etch) method.
Then, with phosphorous oxychloride (POCl
3) making phosphorus diffusion as the gas phase thermal diffusion method of diffuse source, the reverse conductive layer of N-shaped that square resistance is become to 90 Ω/ left and right is formed at the surface of silicon substrate.It should be noted that, remove and be formed at the side of silicon substrate and the reverse conductive layer of rear side with hydrofluoric acid-salpeter solution, afterwards, remove phosphorus glass remaining on the second semiconductor layer with hydrofluoric acid-salpeter solution.
Then, the first passivation layer and the second passivation layer that are made up of aluminium oxide in whole formation of silicon substrate by ALD method form with plasma CVD method the anti-reflection layer 4 being made up of silicon nitride layer on the first passivation layer.The average thickness of the first passivation layer and the second passivation layer is 35nm, and the average thickness of anti-reflection layer is 45nm.
For surface electrode, by silver powder, Al
2o
3-SiO
2-PbO glass frit, the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and the mode that rhodium monomer becomes 0.01 mass parts～0.7 mass parts when silver is made as to 100 mass parts is mixed rhodium monomer wherein, the silver paste agent stencil printing obtaining is applied as to the linear pattern shown in Fig. 1 and makes it dry.
And, apply and make it dry with the pattern of the back side collecting electrodes 6b shown in Fig. 5 aluminium paste in the rear side of silicon substrate.Afterwards, the silver paste agent same with surface electrode 5 being applied as to second shown in Fig. 5 output and taking out the pattern of electrode 6a and make it dry, is to burn till three minutes under the condition of 750 DEG C in maximum temperature.
Make as described above solar cell device.
To rhodium respectively containing proportional, made respectively 30 solar cell devices, measure the output characteristic (photoelectric conversion efficiency) of solar cell device and evaluate.The measurement result of these characteristics is shown in to Fig. 7.The photoelectric conversion efficiency of Fig. 7 is to be made as 100 exponential representation by the content of rhodium as the value of 0.06 mass parts.It should be noted that, the mensuration of these characteristics is according to JIS C 8913, at AM (Air Mass) 1.5 and 100mW/cm
2illuminate condition under measure and obtain mean value.
Result is as shown in Figure 7 known, and the content of rhodium is more than 0.06 mass parts and below 0.5 mass parts, has confirmed that the photoelectric conversion efficiency of solar cell significantly improves.In addition, the content of having confirmed rhodium reaches maximum photoelectric conversion efficiency while being 0.07 mass parts.
< example 2 >
First, use semiconductor substrate same as Example 1, similarly prepared to proceed to electrode with example 1 and formed the substrate that front operation obtains.
Then, formed the electrode of solar element.Surface electrode is by silver powder, Al
2o
3-SiO
2-PbO glass frit, the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and then, as shown in Figure 8, the mode that vanadium monomer becomes 0 mass parts～1.2 mass parts when silver is made as to 100 mass parts is mixed vanadium monomer wherein, the silver paste agent stencil printing obtaining is applied as to the linear pattern shown in Fig. 1 and makes it dry.
And, apply and make it dry with the pattern of the back side collecting electrodes 6b shown in Fig. 5 aluminium paste in the rear side of silicon substrate.Afterwards, with the shape same with surface electrode, silver paste agent being applied as to second shown in Fig. 5 output and taking out the pattern of electrode 6a and make it dry, is to burn till three minutes under the condition of 750 DEG C in maximum temperature.
Make as described above solar cell device.
To each amount of vanadium, make respectively 30 solar cell devices, the constant temperature and moisture test machine that these are dropped into 125 DEG C of temperature, humidity 95%, has measured fill factor, curve factor (FF) sustainment rate after 200 hours.This FF sustainment rate as shown in Figure 8, is that the FF sustainment rate behind 200 hours in the situation of 0.05 mass parts is made as the exponential quantity of 100 o'clock by the content of vanadium.It should be noted that, being determined at according to JIS C 8913 of this characteristic, at AM1.5 and 100mW/cm
2the condition of irradiation under measure and obtain mean value.
Result is as shown in Figure 8 known, confirm that at the content of vanadium be that 0.25 mass parts, FF sustainment rate becomes maximum, scope more than 0.05 mass parts and below 1 mass parts, the variation of the FF sustainment rate after the constant temperature and moisture test of solar cell device diminishes, and contains vanadium effective to the reliability of raising solar cell device with this scope.In addition, the scope FF sustainment rate of the content of also having confirmed vanadium more than 0.2 mass parts and below 0.3 mass parts is especially high.
< example 3 >
Prepare to proceed to electrode by semiconductor substrate same as Example 1, operation and formed the substrate that front operation obtains.
Surface electrode 5 is by silver powder, Al
2o
3-SiO
2-PbO glass frit and the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and then, the mode of composition with the rhodium monomer, rhodium hydrate, rhodium acetylene-derivative and the comparative example 1 that become the embodiment 1～3 that table 1 is represented is mixed wherein, the silver paste agent stencil printing obtaining is applied as to the linear pattern shown in Fig. 1 and makes it dry.
And, apply and make it dry with the pattern of the back side collecting electrodes 6b shown in Fig. 5 aluminium paste in the rear side of silicon substrate.Afterwards, silver paste agent being coated on to second shown in Fig. 5 output and taking out the pattern of electrode 6a and make it dry, is to burn till three minutes under the condition of 750 DEG C in maximum temperature.
Make as described above the solar cell device of embodiment 1～3 and comparative example 1.
About embodiment 1～3 and comparative example 1,30 solar cell devices are made respectively.Output characteristic (fill factor, curve factor (FF) and the highest output (Pmax)) to each solar cell device is measured and is evaluated.The result of these characteristics is shown in table 1.It should be noted that, the mensuration of these characteristics is according to JIS C 8913, at AM1.5 and 100mW/cm
2illuminate condition under measure and obtain mean value.
[table 1]
The each solar cell device FF compared with comparative example 1 that has confirmed embodiment 1～3 is improved, and the output of solar cell device is high.And about the conductivity paste taking silver as principal component, the interpolation of having confirmed rhodium monomer, rhodium hydrate, rhodium organo-metallic compound is effective to improving the photoelectric conversion efficiency of solar cell.
< example 4 >
The substrate that operation before similarly having prepared to proceed to electrode and form with semiconductor substrate same as Example 1, with example 1 obtains.
For the surface electrode of solar cell, by silver powder, Al
2o
3-SiO
2-PbO glass frit and the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and then, by become table 2 illustrated embodiment 4,5 the mode of composition of rhodium monomer, rhodium acetylene derivative compound and comparative example 2 mix wherein, the copper paste stencil printing obtaining is applied as to the linear pattern shown in Fig. 1 and makes it dry.
And, with the pattern of the back side collecting electrodes 6b shown in Fig. 5 at the rear side aluminium coat paste of silicon substrate and make it dry.Afterwards, copper paste application become second shown in Fig. 5 output to take out the pattern of electrode 6a and makes it dry, in blanket of nitrogen, under maximum temperature is the condition of 650 DEG C, burning till three minutes.
Make as described above the solar cell device of embodiment 4,5 and comparative example 2.
About embodiment 4,5 and comparative example 2, make respectively 30 solar cell devices, the output characteristic (fill factor, curve factor (FF) and the highest output (Pmax)) to solar cell device is measured and is evaluated.The measurement result of these characteristics is shown in table 2.It should be noted that, the mensuration of these characteristics is according to JIS C 8913, at AM (1.5 and 100mW/cm
2illuminate condition under measure and obtain mean value.
[table 2]
Confirmed that embodiment 4,5 is compared with comparative example 2, FF is improved, and the output of solar cell device is high.And about the conductivity paste using copper as principal component, the interpolation of having confirmed rhodium monomer, rhodium organo-metallic compound is effective to improving the photoelectric conversion efficiency of solar cell.Especially the interpolation of, having confirmed rhodium organo-metallic compound is effective to improving the photoelectric conversion efficiency of solar cell.
< example 5 >
The substrate of the operation before similarly having prepared to proceed to electrode and form with semiconductor substrate same as Example 1, with example 1.
For the surface electrode 5 of solar cell device, by silver powder and copper powders, Al
2o
3-SiO
2-PbO glass frit and the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and then, the mode that becomes the rhodium acetylene derivative compound of the embodiment 6,7 shown in table 3 and table 4 and the composition of comparative example 3,4 is mixed, the paste obtaining is applied as to the linear pattern shown in Fig. 1 with stencil printing and makes it dry.
And 9b side overleaf, with the pattern aluminium coat paste of the back side collecting electrodes 6b shown in Fig. 5 and make it dry.Afterwards, the agent of copper silver paste is applied as to second shown in Fig. 5 output and takes out the pattern of electrode 6a and make it dry, in blanket of nitrogen, under maximum temperature is the condition of 750 DEG C, burn till three minutes.
Make as described above solar cell device.
About embodiment 6,7 and comparative example 3,4, make respectively 30 solar cell devices, the output characteristic (fill factor, curve factor (FF) and the highest output (Pmax)) to solar cell device is measured and is evaluated.The result of these characteristics is shown in table 3 and table 4.It should be noted that, the mensuration of these characteristics is according to JIS C 8913, at AM1.5 and 100mW/cm
2illuminate condition under measure and obtain mean value.
[table 3]
* 1: the mass parts of rhodium when Ag and Cu are made as to 100 mass parts
[table 4]
* 1: the mass parts of rhodium when Ag and Cu are made as to 100 mass parts
The embodiment 6,7 that has confirmed table 3 and table 4 compares with the comparative example 3,4 of comparing with it, and FF is improved, and the output of solar cell device is high.And, about using silver and copper as the conductivity paste of principal component, confirmed that the interpolation of rhodium organo-metallic compound is effective to the photoelectric conversion efficiency of raising solar cell device.
< example 6 >
The substrate that use semiconductor substrate same as Example 1, operation before similarly having prepared to proceed to electrode and form with example 1 obtains.
For the surface electrode of solar cell device, by silver powder, Al
2o
3-SiO
2-PbO glass frit and the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and then, mode with the composition that becomes the embodiment 1,2 shown in table 5 and comparative example is mixed wherein, the silver paste agent stencil printing obtaining is applied as to the linear pattern shown in Fig. 1 and makes it dry.
And, with the pattern of the back side collecting electrodes 6b shown in Fig. 5 at the rear side aluminium coat paste of silicon substrate and make it dry.Afterwards, silver paste agent being applied as to second shown in Fig. 5 output and taking out the pattern of electrode 6a and make it dry, is to burn till three minutes under the condition of 750 DEG C in maximum temperature.
Make as described above solar cell device 10.About embodiment 8,9 and comparative example 5, make respectively 30 solar cell devices 10, measure the fill factor, curve factor (FF) of the output characteristic of solar cell device.And then by the constant temperature and moisture test machine of these 125 DEG C of temperature of input, humidity 95%, measure the sustainment rate of the fill factor, curve factor (FF) after 200 hours and after 350 hours.This sustainment rate is that the FF value at initial stage is made as to the value that represents the sustainment rate after 200 hours and after 350 hours in 100% situation with percentage.It should be noted that, the mensuration of these characteristics is according to JIS C 8913, at AM1.5 and 100mW/cm
2the condition of irradiation under measure and obtain mean value.
[table 5]
As shown in Figure 5, rhodium and vanadium are made an addition in the embodiment 8 of silver paste agent, in constant temperature and moisture test, with comparative example 5 and only add compared with the embodiment 9 of rhodium, its FF sustainment rate is large.Confirm that thus reliability is improved compared with other.So, confirmed that both interpolations of rhodium and vanadium produce effect to improving FF sustainment rate and improving reliability.
< example 7 >
Then, use semiconductor substrate same as Example 1, similarly prepared to proceed to electrode with example 1 and formed the substrate that front operation obtains.
For the surface electrode of solar cell device, by silver powder, Al
2o
3-SiO
2-PbO glass frit and the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and then, mode with the composition that becomes the embodiment 10～21 shown in table 6 is mixed wherein, the silver paste agent stencil printing obtaining is applied as to the linear pattern shown in Fig. 1 and makes it dry.
And, with the pattern of the back side collecting electrodes 6b shown in Fig. 5 at the rear side aluminium coat paste of silicon substrate and make it dry.Afterwards, silver paste agent being applied as to second shown in Fig. 5 output and taking out the pattern of electrode 6a and make it dry, is to burn till three minutes under the condition of 750 DEG C in maximum temperature.
Make as described above solar cell device, about embodiment 10～21, made respectively 30 solar cell devices, measured the fill factor, curve factor (FF) of the output characteristic of these solar cell devices.And then these solar cell devices are dropped into the constant temperature and moisture test machine of 125 DEG C of temperature, humidity 95%, measure the sustainment rate of the fill factor, curve factor (FF) after 200 hours and after 350 hours.This sustainment rate is that the FF value at initial stage is made as in 100% situation, represents the value of the sustainment rate after 200 hours and after 350 hours with percentage.It should be noted that, the mensuration of these characteristics is according to JIS C 8913, at AM1.5 and 100mW/cm
2illuminate condition under measure and obtain mean value.
[table 6]
Especially confirmed in the time that silver is made as to 100 mass parts from these results, in the situation more than the content of glass dust is made as 1 mass parts and below 15 mass parts, the FF value at initial stage is high, and FF sustainment rate is also high.And then the content of having confirmed glass dust be above and 6.5 mass parts of 4.5 mass parts when following the FF value at initial stage high and FF sustainment rate is best.
< example 8 >
Then, use semiconductor substrate same as Example 1, similarly prepared to proceed to electrode with example 1 and formed the substrate that front operation obtains.
For the surface electrode of solar cell device, silver powder, vanadium and rhodium are carried on to the surperficial Al of most glass particles
2o
3-SiO
2-PbO glass frit, the organic carrier ratio taking mass ratio as 85:5:10 is mixed, and then, mode with the composition that becomes the embodiment 22 shown in table 7 and comparative example 6 is mixed wherein, the silver paste agent stencil printing obtaining is applied as to the linear pattern shown in Fig. 1 and makes it dry.
And, with the pattern of the back side collecting electrodes 6b shown in Fig. 5 at the rear side aluminium coat paste of silicon substrate and make it dry.Afterwards, after silver paste agent is applied as to second shown in Fig. 5 output and takes out the pattern of electrode 6a and make it dry, be to burn till three minutes under the condition of 750 DEG C in maximum temperature.
Make as described above solar cell device.About embodiment 22 and comparative example 6, make respectively 30 solar cell devices, measure the fill factor, curve factor (FF) of the output characteristic of solar cell device.And then these solar cell devices are dropped into the constant temperature and moisture test machine of 125 DEG C of temperature, humidity 95%, measure the sustainment rate of the fill factor, curve factor (FF) after 200 hours and after 350 hours.This sustainment rate is that the FF value at initial stage is made as in 100% situation, represents the value of the sustainment rate after 200 hours and after 350 hours with percentage.It should be noted that, the mensuration of these characteristics is according to JIS C 8913, at AM1.5 and 100mW/cm
2illuminate condition under measure and obtain mean value.
[table 7]
From these results verifications the FF sustainment rate of embodiment 22 also higher 350 hours, FF sustainment rate is also high compared with the embodiment 8 of example 6.So, confirm to make vanadium and rhodium to be carried on the surface of glass particle, improved FF sustainment rate.
It should be noted that, the above embodiments is only a few one example, about niobium and the tantalum of the 5th family's element except vanadium, also similar in chemical property etc. with vanadium, about the rhenium except rhodium and osmium, also similar in same chemical property etc. with rhodium, therefore, in conductivity paste, add these metallic elements, also can obtain the result roughly the same with the present embodiment.
Claims (13)
1. the electrode of a solar cell conductivity paste, has:
The glass dust being formed by most glass particles; With
Using at least one in silver and copper as principal component and be added with the non-glass composition of following metal element A 1, wherein,
At least one for selecting from vanadium, niobium, tantalum, rhodium, rhenium, osmium of metal element A 1.
2. the electrode of solar cell according to claim 1 conductivity paste, wherein,
In described non-glass composition, be added with following metal element A 2 and following metal element A 3 as described metal element A 1,
At least one for selecting from vanadium, niobium, tantalum of metal element A 2.
At least one for selecting from rhodium, rhenium, osmium of metal element A 3.
3. the electrode of solar cell according to claim 1 conductivity paste, wherein,
In described non-glass composition, be added with at least one in vanadium and rhodium as described metal element A 1.
4. the electrode of solar cell according to claim 1 conductivity paste, wherein,
There is described metal element A 1 at described glass particle and the area load that becomes at least one party in the metal of described principal component of described non-glass composition.
5. the electrode of solar cell according to claim 2 conductivity paste, wherein,
There are described metal element A 2 and described metal element A 3 at described glass particle and the area load that becomes at least one party in the metal of described principal component of described non-glass composition.
6. the electrode of solar cell according to claim 5 conductivity paste, wherein,
Described metal element A 2 is vanadium, and described metal element A 3 is rhodium.
7. the electrode of solar cell according to claim 3 conductivity paste, wherein,
In described non-glass composition, be added with vanadium as described metal element A 1, with respect at least one 100 mass parts of silver and copper, contain the above and vanadium below 1 mass parts of 0.05 mass parts.
8. the electrode of solar cell according to claim 3 conductivity paste, wherein,
In described non-glass composition, be added with rhodium as described metal element A 1, with respect at least one 100 mass parts of silver and copper, contain the above and rhodium below 0.5 mass parts of 0.06 mass parts.
9. the electrode of solar cell according to claim 1 conductivity paste, wherein,
In described glass particle, contain at least one metallic element of selecting from vanadium, niobium, tantalum, be added with from rhodium, rhenium, osmium, select at least one as described metal element A 1.
10. the electrode of solar cell according to claim 9 conductivity paste wherein, contains vanadium in described glass particle, is added with rhodium as described metal element A 1.
The electrode of 11. solar cells according to claim 10 conductivity paste, wherein,
In described glass particle, with respect to 100 mass parts of described glass dust, the vanadium more than containing 0.2 mass parts and below 20 mass parts, in described non-glass composition, with respect at least one 100 mass parts of silver and copper, contain the above and rhodium below 1.2 mass parts of 0.06 mass parts.
12. 1 kinds of solar cells, possess:
Semiconductor substrate;
Be disposed at the antireflection film of the first area on an interarea of this semiconductor substrate; With
Be disposed at the electrode that the electrode conductivity paste of the solar cell described in any one second area, that burn till claim 1～11 in conduct on an interarea of the described semiconductor substrate region different from described first area forms.
The manufacture method of 13. 1 kinds of solar cells, wherein,
This solar cell possesses semiconductor substrate, be disposed at the antireflection film of the first area on an interarea of this semiconductor substrate and be disposed at the electrode of the second area in conduct on an interarea of the described semiconductor substrate region different from first area,
The manufacture method of described solar cell has:
On an interarea of described semiconductor substrate, form the first operation of described antireflection film;
The electrode of the solar cell described in any one of claim 1～11 is disposed to the second operation on described antireflection film with conductivity paste with electrode pattern;
Remove by burning till described electrode conductivity paste the described antireflection film being positioned under this electrode conductivity paste, described antireflection film is disposed to the described first area of described semiconductor substrate, and forms the 3rd operation of described electrode conductivity paste being burnt till to the described electrode forming at the described second area of described semiconductor substrate.
Applications Claiming Priority (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012042237 | 2012-02-28 | ||
| JP2012-042237 | 2012-02-28 | ||
| JP2012-122329 | 2012-05-29 | ||
| JP2012122329 | 2012-05-29 | ||
| JP2012168327 | 2012-07-30 | ||
| JP2012-168327 | 2012-07-30 | ||
| JP2012189176 | 2012-08-29 | ||
| JP2012-189176 | 2012-08-29 | ||
| JP2012214455 | 2012-09-27 | ||
| JP2012-214455 | 2012-09-27 | ||
| JP2012-239976 | 2012-10-31 | ||
| JP2012239976 | 2012-10-31 | ||
| PCT/JP2013/055434 WO2013129578A1 (en) | 2012-02-28 | 2013-02-28 | Conductive paste for solar cell electrodes, solar cell, and method for manufacturing solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104137274A true CN104137274A (en) | 2014-11-05 |
| CN104137274B CN104137274B (en) | 2016-09-21 |
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| CN201380011267.4A Active CN104137274B (en) | 2012-02-28 | 2013-02-28 | The electrode of solaode electric conductivity unguentum, solaode and the manufacture method of solaode |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20150047700A1 (en) |
| JP (1) | JP5883116B2 (en) |
| CN (1) | CN104137274B (en) |
| WO (1) | WO2013129578A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107026211A (en) * | 2015-03-30 | 2017-08-08 | 亚特比目株式会社 | The manufacture method of solar cell and solar cell |
| CN107527957A (en) * | 2016-06-20 | 2017-12-29 | 茂迪股份有限公司 | Solar cell receiving light on one side, manufacturing method thereof and solar cell module |
| CN113582693A (en) * | 2021-08-04 | 2021-11-02 | 湖南省美程陶瓷科技有限公司 | Ceramic atomized sheet material and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016532317A (en) * | 2013-09-27 | 2016-10-13 | ダンマークス テクニスク ユニバーシテットＤａｎｍａｒｋｓ Ｔｅｋｎｉｓｋｅ Ｕｎｉｖｅｒｓｉｔｅｔ | Nanostructured silicon-based solar cell and method for producing nanostructured silicon-based solar cell |
| US9293611B1 (en) * | 2014-09-24 | 2016-03-22 | Huey-Liang Hwang | Solar cell structure and method for fabricating the same |
| JP6336139B2 (en) * | 2015-02-02 | 2018-06-06 | 京セラ株式会社 | Solar cell element and manufacturing method thereof |
| DE102015110851B4 (en) * | 2015-07-06 | 2019-01-03 | Hanwha Q Cells Gmbh | Solar cell, solar cell string and solar cell manufacturing process |
| KR101680037B1 (en) * | 2015-07-28 | 2016-12-12 | 엘지전자 주식회사 | Solar cell and solar cell panel including the same |
| CN114551610B (en) * | 2022-03-11 | 2024-05-31 | 广东爱旭科技有限公司 | Solar cell, electrode structure, cell assembly, power generation system and preparation method |
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| JP2011517117A (en) * | 2008-04-09 | 2011-05-26 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conductive composition and method of use in the manufacture of semiconductor devices |
| TWI448444B (en) * | 2010-08-11 | 2014-08-11 | Hitachi Ltd | A glass composition for an electrode, a paste for an electrode for use, and an electronic component to which the electrode is used |
| CN103547542A (en) * | 2011-03-24 | 2014-01-29 | E.I.内穆尔杜邦公司 | Conductive paste composition and semiconductor devices made therewith |
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2013
- 2013-02-28 JP JP2014502372A patent/JP5883116B2/en active Active
- 2013-02-28 CN CN201380011267.4A patent/CN104137274B/en active Active
- 2013-02-28 US US14/381,961 patent/US20150047700A1/en not_active Abandoned
- 2013-02-28 WO PCT/JP2013/055434 patent/WO2013129578A1/en active Application Filing
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| CN101189719A (en) * | 2005-06-03 | 2008-05-28 | 费罗公司 | Lead free solar cell contacts |
| CN102150220A (en) * | 2008-09-10 | 2011-08-10 | E.I.内穆尔杜邦公司 | Solar cell electrodes |
| JP2010251645A (en) * | 2009-04-20 | 2010-11-04 | Namics Corp | Solar cell, and conductive paste for forming electrode of the same |
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| CN107026211A (en) * | 2015-03-30 | 2017-08-08 | 亚特比目株式会社 | The manufacture method of solar cell and solar cell |
| CN107527957A (en) * | 2016-06-20 | 2017-12-29 | 茂迪股份有限公司 | Solar cell receiving light on one side, manufacturing method thereof and solar cell module |
| CN113582693A (en) * | 2021-08-04 | 2021-11-02 | 湖南省美程陶瓷科技有限公司 | Ceramic atomized sheet material and preparation method thereof |
| CN113582693B (en) * | 2021-08-04 | 2022-07-12 | 湖南省美程陶瓷科技有限公司 | Ceramic atomized sheet material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20150047700A1 (en) | 2015-02-19 |
| JP5883116B2 (en) | 2016-03-09 |
| WO2013129578A1 (en) | 2013-09-06 |
| CN104137274B (en) | 2016-09-21 |
| JPWO2013129578A1 (en) | 2015-07-30 |
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